US9422433B2 - Ternary antifouling compositions and methods - Google Patents

Ternary antifouling compositions and methods Download PDF

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US9422433B2
US9422433B2 US14/575,625 US201414575625A US9422433B2 US 9422433 B2 US9422433 B2 US 9422433B2 US 201414575625 A US201414575625 A US 201414575625A US 9422433 B2 US9422433 B2 US 9422433B2
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US20150307720A1 (en
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Karen L. Wooley
Jeffery E. Raymond
Kevin A. Pollack
Philip M. Imbesi
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Texas A&M University System
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect

Definitions

  • the method of prevention has been through the use of anti-biofouling paints and coatings which release biocides, such as cuprous oxide and tributyltin; however, due to the negative effects these chemicals have on the environment, the use of these systems is in decline.
  • Fluoropolymers, siloxanes and poly(ethylene glycol) (PEG) have been researched extensively as anti-biofoulers due to their unique chemical compositions. Fluoropolymers are of particular interest due to a low surface energy, low wettability and chemical stability. Siloxanes, specifically poly(dimethylsiloxane) (PDMS), have shown anti-biofouling attributes due to their inertness, stability, and pliability. Commercially, PDMS coatings are marketed as non-toxic marine coatings due to the release and rejection of fouling agents under suitable hydrodynamic conditions. Poly(ethylene glycol) (PEG), or poly(ethylene oxide) (PEO), has been used extensively in the field of marine applications, as well as in the medical field due to its ability to generate surfaces that resist non-specific protein adsorption.
  • PEG poly(ethylene glycol)
  • PEO poly(ethylene oxide)
  • Biofouling can result from a number of mechanisms but generally involves protein adhesion and deposition by microorganisms or organisms to surfaces exposed to, and typically in fluid communication with, an environment which harbors the microorganisms or organisms.
  • biomass adhesion and deposition by microorganisms or organisms to surfaces exposed to, and typically in fluid communication with, an environment which harbors the microorganisms or organisms.
  • the costs associated with maintenance, increased vessel drag, and other consequences of biofouling are billions of dollars per year.
  • Fluoropolymers, siloxanes and poly(ethylene glycol) (PEG) have been researched as anti-biofoulers due to their unique chemical compositions. Fluoropolymers are of particular interest due to a low surface energy, low wettability and chemical stability.
  • Siloxanes, specifically poly(dimethylsiloxane) (PDMS) have shown anti-biofouling attributes due to their inertness, stability, and pliability.
  • PDMS coatings are marketed as non-toxic marine coatings due to the release and rejection of fouling agents under suitable hydrodynamic conditions.
  • Poly(ethylene glycol) (PEG) has been used extensively in the field of marine applications, as well as in the medical field due to its ability to generate surfaces that resist non-specific protein adsorption.
  • linear PDMS has been modified to include hydrophilic and fluorinated moieties.
  • the chemistries involved incorporation of linear PDMS backbones with chemical variation achieved via side group modification. This approach is limited, as it does not address the topological influences of surfaces in preventing biofouling. Topological heterogeneity in conjunction with chemical heterogeneity can further improve anti-biofouling performance through the inhibition of adhesive proteins that settle on the surface. Therefore, there remains a need for anti-biofouling compounds possessing significant topological and chemical heterogeneity.
  • the disclosed subject matter provides terpolymers of hyperbranched fluoropolymers, PEG and PDMS to mitigate biofouling in various applications.
  • a compound of Formula A as illustrated and below is provided:
  • the compound of Formula A is represented by Compound Q, which is defined to have the formula of FIG. 21 , wherein n is selected from an integer between 1 and 15 inclusive, and p and q are independently selected from an integer between 1 and 250 inclusive.
  • a method for reducing biofouling of a surface includes providing a terpolymer according to Formula A above to a surface susceptible to biofouling.
  • a method for preparing a compound for reducing fouling of a crude hydrocarbon in a hydrocarbon refining process includes:
  • n is selected from an integer between 1 and 15 inclusive;
  • n is selected from an integer between 1 and 15 inclusive;
  • a method for mitigating biofouling of a surface includes providing a surface susceptible to biofouling and contacting the surface with a compound represented by Formula A.
  • a composition comprising Formula for mitigating biofouling of a surface is provided.
  • compositions comprising the compound identified above, and products incorporating compositions comprising the compound identified above.
  • FIG. 1 is a schematic illustration of a synthesis protocol for a terpolymer of HBFP-PEG-PDMS.
  • FIG. 2 illustrates gel permeation chromatography curves for the HBFPs as synthesized in Example 1.
  • FIG. 3 illustrates tapping mode atomic force microscopy images of terpolymer networks according to weight percent PDMS and PEG relative to the weight of the HBFP.
  • FIGS. 4A and 4B are contour graphs of static water contact angle measurements.
  • FIG. 4A is a contour graph of static water contact angle measurement of a dry film.
  • FIG. 4B is a contour graph of static water contact angle measurement on a water-saturated film.
  • FIG. 5 is a contour graph of the differential static contact angle between dry and water-saturated terpolymer films.
  • FIGS. 6A-6E are topography and surface force spectroscopy micrographs of a HBFP-PEG-PDMS terpolymer network.
  • FIG. 6A is an AFM micrograph of the topography of the HBFP-PEG-PDMS terpolymer network (4 ⁇ m 2 field of view).
  • FIG. 6B is a surface force spectroscopy map of surface modulus of the HBFP-PEG-PDMS terpolymer network, with relative modulus superimposed over network topography in perspective view.
  • FIG. 6C is a surface force spectroscopy map of deformation of the HBFP-PEG-PDMS terpolymer network, with deformation superimposed over a three-dimensional rendering of network topography in perspective view.
  • FIG. 6A is an AFM micrograph of the topography of the HBFP-PEG-PDMS terpolymer network (4 ⁇ m 2 field of view).
  • FIG. 6B is a surface force spectroscopy map of surface modulus of the
  • FIG. 6D is a surface force spectroscopy map of relative adhesion force of the HBFP-PEG-PDMS terpolymer network, with relative adhesion force superimposed over a three-dimensional rendering of network topography in perspective view.
  • FIG. 6E is a surface force spectroscopy map of relative dissipation of the HBFP-PEG-PDMS terpolymer network, with relative dissipation superimposed over a three-dimensional rendering of network topography in perspective view.
  • FIG. 7A illustrates attenuated total reflectance infrared spectroscopy spectra for a 2:1:1 HBFP-PEG-PDMS terpolymer network.
  • FIG. 7B illustrates X-ray photoelectron spectra for a 2:1:1 HBFP-PEG-PDMS terpolymer network.
  • FIG. 8 is a thermogravimetric analysis trace of a HBFP-PEG-PDMS terpolymer network.
  • FIG. 9A is a differential scanning calorimetry trace of a HBFP-PEG-PDMS terpolymer network.
  • FIG. 9B is an expanded trace of the HBFP-PEG-PDMS terpolymer network.
  • FIG. 10A is a dynamic thermal mechanical analysis graph of a HBFP-PEG-PDMS terpolymer network.
  • FIG. 10B is a dynamic mechanical analysis graph of the HBFP-PEG-PDMS terpolymer network.
  • FIGS. 11A-C are dynamic thermal mechanical analysis graph of a HBFP-PEG-PDMS terpolymer network.
  • FIG. 11A is a graph of storage modulus and temperature vs. time;
  • FIG. 11B is a graph of loss modulus and tan ⁇ vs. time;
  • FIG. 11C is a graph of total change in modulus per unit change in temperature v. temperature.
  • FIG. 12 is submersion dynamic mechanical analysis plot of a HBFP-PEG-PDMS terpolymer network at 37° C. in PBS.
  • FIG. 13A is an illustration of fluorescence signal intensities before and after BSA incubation.
  • FIG. 13B is a representative confocal photomicrograph for a PDMS standard network.
  • FIG. 13C is a representative confocal photomicrograph for a HBFP-PEG-PDMS terpolymer network.
  • FIG. 14 is a graph of initial attachment of diatoms on HBFP-PEG-PDMS terpolymer coatings having various compositions.
  • FIG. 15 is a graph of water channel removal of diatoms on HBFP-PEG-PDMS terpolymer coatings having various compositions.
  • FIG. 16 is a graph of density of diatoms remaining after water channel removal from HBFP-PEG-PDMS terpolymer coatings having various compositions.
  • FIG. 17 is a graph of spore settlement on HBFP-PEG-PDMS terpolymer coatings having various compositions.
  • FIG. 18 is a graph of sporeling growth on HBFP-PEG-PDMS terpolymer coatings having various compositions.
  • FIG. 19 is a graph of water channel removal of sporelings from HBFP-PEG-PDMS terpolymer coatings having various compositions.
  • FIG. 20A illustrates growth of sporelings on HBFP-PEG-PDMS terpolymer coatings having various compositions after 7 days.
  • FIG. 20B illustrates sporelings remaining after exposure to shear stress of 160 kPa.
  • FIG. 21 is the structural chemical formula of Compound Q.
  • FIG. 22 is the structural chemical formula of HBFP(I).
  • FIG. 23 is the structural chemical formula of HBFP(II)
  • FIG. 24 is the structural chemical formula of HBFP(III).
  • FIG. 25 is the structural chemical formula of HBFP(IV).
  • FIG. 26 is the structural chemical formulas of Reaction Scheme 4.
  • biofouling generally refers to the accumulation of undesired organisms, microorganisms, and proteins on surfaces exposed to environments where microorgansisms and organisms reside.
  • surface susceptible to biofouling generally refers to any surface exposed or potentially exposed to an environment where microorganisms and organisms reside, and refers to both internal and external surfaces so exposed.
  • mitigation of biofouling is generally achieved when the susceptibility of a surface to microorganism, organism and/or protein adhesion is reduced, or when the force required to remove adhered microorganisms, organisms and/or proteins is reduced, or when the overall degree of biofouling observed for a surface is reduced relative to a similar surface in a similar environment.
  • reference to a group being a particular polymer encompasses polymers that contain primarily the respective monomer along with negligible amounts of other substitutions and/or interruptions along polymer chain.
  • reference to a group being a polyethylene glycol group does not require that the group consist of 100% ethylene glycol monomers without any linking groups, substitutions, impurities or other substituents (e.g., alkylene substituents).
  • Such impurities or other substituents can be present in relatively minor amounts so long as they do not affect the functional performance of the compound, as compared to the same compound containing the respective polymer substituent with 100% purity.
  • a terpolymer is a polymer comprising at least three different polymer substitutents (such as PEG, PDMS, and HBFP).
  • a terpolymer comprising a hyperbranched fluropolymer comprising a hyperbranched fluropolymer.
  • Suitable HBFPs include, but are not limited to, HBFP(I) ( FIG. 21 ), HBFP(II) ( FIG. 22 ), HBFP(III) ( FIG. 23 ), and HBFP(IV) ( FIG. 24 ) and derivatives thereof.
  • HBFPs may be synthesized using methods known in the art. See Bartels, J. W.; Cheng, C.; Powell, K. T.; Xu, J.; Wooley, K. L. Macromol. Chem. Phys . 2007, 208, 1676, the disclosure of which is incorporated by reference.
  • Suitable hydrophilic polymer components can be of neutral, anionic, cationic or zwitterionic charge character, and include, for example, PEG and PEG derivatives (e.g., bisamino-propyl PEG), poly(N-vinylpyrolidinone), polyacrylamide, poly(acrylic acid), polyethyleneimine, polycarboxybetaine, polysulfobetaine, and derivatives thereof.
  • Hydrophilic polymers have an affinity for water, as measured by a low water contact angle ( ⁇ 30°), and/or swellability or solubility in water.
  • the amount of hydrophilic polymer component may vary.
  • the hydrophobic component may vary between 0-75 wt %, calculated with respect to the weight of the HBFP-containing component.
  • the hydrophilic polymer component may be linear or branched.
  • Suitable hydrophobic polymer components include, for example, PDMS and PDMS derivatives (e.g., bisamino-propyl PDMS), polyisoprene, Bolton hyperbranched polyesters, poly(methyl (meth)acrylate), polystyrene, and derivatives thereof.
  • Hydrophobic polymers lack an affinity for water, as measured by a high water contact angle (>90°).
  • the amount of hydrophobic components may vary.
  • the hydrophobic polymer component may vary between 0-75 wt %, calculated with respect to the weight of the HBFP-containing component.
  • the hydrophobic polymer component may be linear or branched.
  • the hydrophilic components and hydrophobic components form crosslinks with the HBFP-containing components.
  • Such crosslinking provides a three-dimensional network from the otherwise low-viscosity, HBFP.
  • the crosslinking with either hydrophilic or hydrophobic components creates an amphiphilic coating possessing chemical and surface heterogeneity on both the nano- and micro-scales.
  • crosslinks may form via a substitution reaction of the bromoacetyl and bromobenzyl groups of HBFP with the amine termini of both the linear PEG and PDMS crosslinkers and crosslinking may be affected through a deposition followed by a thermal curing.
  • photo-chemically-initiated thiol-ene reactions or other typical chemical reactions are used to form the crosslinks, for suitably-functionalized HBFP, hydrophilic and hydrophobic polymer components.
  • compositions comprising the reaction product of a hyperbranched fluoropolymer (HBFP)-containing component, a hydrophilic polymer component, and a hydrophobic polymer component.
  • HBFP hyperbranched fluoropolymer
  • the compound of Formula A is represented by Compound Q, which is defined to have the formula of FIG. 21 , wherein n is selected from an integer between 1 and 15 inclusive, and p and q are independently selected from an integer between 1 and 250 inclusive.
  • a method for reducing biofouling of a surface includes providing a terpolymer according to Formula A above to a surface susceptible to biofouling.
  • a method for preparing a compound for mitigating biofouling includes:
  • n is selected from an integer between 1 and 15 inclusive;
  • n can be selected from an integer between 1 and 15 inclusive
  • x can be selected from a number between 0.01 and 0.99
  • y (1 ⁇ x)
  • m, q, and p can be independently selected from an integer between 1 and 250 inclusive
  • the HBFP precursor can be generated by nucleophilic aromatic substitution of 2,3,4,5,6-pentafluorostyrene with excess polyethylene glycol in the presence of sodium hydride and tetrahyrofuran at 0 degrees Celsius followed by maintenance at room temperature in a nitrogen gas atmosphere for 14 hours, as shown in reaction scheme 1 below.
  • the product of scheme one can be esterified by reaction with 2-bromopropionyl bromide in triethylamine and tetrahydrofuran at 0 degrees Celsius followed by stirring at room temperature for 16 hours in a nitrogen gas atmosphere, as shown in scheme 2 below.
  • the inimer product of Reaction Scheme 2 can be copolymerized via CuBr and PMDETA catalysis to promote atom transfer radical condensation vinyl copolymerization to generate HBFP as shown in Reaction Scheme 3 below.
  • the HBFP product of Reaction Scheme 3 can subsequently be crosslinked with bis(3-aminopropyl)-terminated PEG and bis(3-aminopropyl-terminated PDMS via Reaction Scheme 4 shown in FIG. 26 .
  • the weight percent of the PEG in the terpolymer can be between about 0.5% and about 99% of the total weight of the terpolymer compound.
  • the weight percent of polyethylene glycol relative to the terpolymer is between about 10% and about 90%, and in still further embodiments, the weight percent is between about 15% and about 35%.
  • the weight percent of the PDMS can be between about 0.5% and about 99% of the total weight of the terpolymer compound.
  • the weight percent of polyethylene glycol relative to the terpolymer is between about 10% and about 90%, and in still further embodiments, the weight percent is between about 15% and about 35%.
  • the HBFP-PEG-PDMS terpolymers of the present disclosure can be characterized by a heterogeneous distribution of chemical domains.
  • certain HBFP-PEG-PDMS terpolymers display heterogenous, patch-work patterns of hydrophobic (e.g., low surface energy) and hydrophilic (e.g., water soluble and swellable) domains.
  • hydrophobic, or rigid, domains with hydrophilic, or dynamic, domains provides a material capable of, among other things, reducing or preventing biofouling, and/or promoting foulant release and removal.
  • certain HBFP-PEG-PDMSs may be characterized by increased fluorine content at the surface of the material.
  • the HBFP-PEG-PDMS of the present disclosure may be characterized by a micro- and nanoscopically-resolved topography.
  • Topographical heterogeneity at the nanoscale may, among other things, prevent or reduce protein and/or polysaccharide adhesion.
  • Topographical heterogeneity at the microscale may, among other things, prevent or reduce organism adhesion.
  • nano- and microscale topographical heterogeneity may synergistically work to prevent biofouling.
  • the HBFP-PEG-PDMS of the present disclosure may be characterized by a heterogeneous distribution of structural domains.
  • certain HBFP-PEG-PDMSs display heterogeneous, patch-work patterns of hydrophobic (e.g., rigid or hard) and hydrophilic (e.g., soft, dynamic or swellable) domains.
  • hydrophobic e.g., rigid or hard
  • hydrophilic e.g., soft, dynamic or swellable domains.
  • the combination of domains with these properties provides a material capable of, among other things, reducing or preventing biofouling.
  • the HBFP-PEG-PDMS of the present disclosure may show dynamic surface reorganization upon immersion in water, as measured by static water contact angle.
  • the HBFP-PEG-PDMS of the present disclosure may comprise a raised region, wherein the raised region is characterized by a high modulus, a low deformation, a low surface energy, and low dissipation; a lattice region, wherein the lattice region is characterized by a moderate modulus, a moderate deformation, a low surface energy, and a moderate dissipation; and a deeper interstitial region, wherein the deeper interstitial region is characterized by a low modulus, a high deformation, a high surface energy, and a high dissipation.
  • the dynamic and heterogeneous topology of the disclosed compounds has significant functional consequences in biofouling mitigation applications. Any fouling that occurs upon a substrate involves balancing of particular molecular-level attractive and repulsive interactions between the foulant and the surface. Marine organisms initially probe surfaces, decide whether or not to settle on either a hydrophobic, hydrophilic, soft or hard substrate and adhere by the secretion of adhesin proteins. In biomedical applications of materials, many different types of biomolecules and biomacromolecules make contact with the substrate, depending on the particular mechanism and site of administration. In other applications of anti-fouling coatings, the foulants may be various biological or synthetic chemicals encountered in the environment. Different fouling species experience different binding interactions with different anti-fouling coatings components.
  • polymer networks that present compositionally, topographically and morphologically-heterogeneous surfaces, therefore, a complex profile of attractive and repulsive interactions is provided, to limit the dimensions over which adhesion may occur.
  • the characteristic of dynamic reorganization of the surface components is a mechanism by which to alter the composition, topography, morphology features that are presented from the surface and, thereby, detach any initially adhered species, or to intercept and prevent their adhesion before it occurs.
  • the combination of a complex surface that is capable of in situ reorganization is a powerful and unique concept toward anti-fouling coatings that exhibit exceptional anti-foulant and foulant-releasing performance.
  • the various topographical characterizations of the embodiments disclosed herein support a varied and dynamic topology for biofouling mitigation applications.
  • static surface contact angle measurements before and after water equilibration of these ternary systems provide compelling evidence of dynamic reordering in these systems.
  • the formulation e.g. PDMS and PEG ratios to HBFP
  • the system can be tailored to express greater amounts of hydrophobicity or hydrophilicity on exposure to water and sea water.
  • DMA environmental dynamic mechanical analysis
  • compositions that mitigate biofouling can be used in compositions that mitigate biofouling.
  • suitable compositions for the disclosed compounds include surface coatings, including anti-fouling coatings for any surface that is placed in contact with a marine environment, biological fluid, or the environment.
  • the disclosed compounds are suitable for coatings for maritime vessels, undersea cables, lenses for sonar and other instruments, glass or plastic windows, solar panels, food packaging materials, catheters, i.v. needles, medical implants, stents, heart valves, pacemakers, pacemaker wires, and any other body-implantable device.
  • the compositions can further contain adhesion agents, such as epoxides, dispersants, and stabilizers.
  • compositions of the disclosed subject matter can further include, for example, lubricants, corrosion inhibitors, and reduced-friction surface coatings.
  • additives of the disclosed subject matter can be added with other compatible components that address other problems that can present themselves in an oil refining process known to one of ordinary skill in the art.
  • the compounds of the disclosed subject matter can be incorporated into surface coatings and surface adhesives for disposition over the surface of an article.
  • the compounds are applied by means of dropping, painting, or pouring a solution containing the compounds onto the surface.
  • the compounds can be spray coated over the surface of an article susceptible to biofouling. Coatings incorporating the disclosed compounds can be applied before first exposure of a surface to biofouling or during the life of the surface after initial exposure to biofouling.
  • one aspect of the disclosed subject matter provides a method of reducing and/or preventing, in particular, biofouling that includes adding at least one compound of the disclosed subject matter to a surface that is known to or believed to be susceptible to biofouling.
  • a method to mitigate biofouling comprising adding any one of the above-mentioned compounds to a coating for a surface that is susceptible to biofouling.
  • the total amount of the compound to be added to a coating or applied directly to a surface can be determined by a person of ordinary skill in the art. In one embodiment, substantially the entire surface susceptible to biofouling is coated with the compound.
  • the compounds of the disclosed subject matter can be added to a coating solution in a solid (e.g. powder or granules) or liquid form directly to the coating solution.
  • a solid e.g. powder or granules
  • Any suitable technique can be used for adding the compound to a coating solution, as known by a person of ordinary skill in the art in view of the process to which it is employed.
  • Monomers and polymers were characterized by 1 H, 13 C and 19 F nuclear magnetic resonance (NMR) spectroscopies using a Varian Inova 300 spectrometer.
  • 1 H and 13 C NMR spectra were analyzed using the solvent signal as an internal reference and 19 F NMR spectra were analyzed with CF 3 COOH as an external standard.
  • High-resolution mass spectrometry (HRMS) for the monomers was conducted on an Applied Biosystems PE SCIEX QSTAR. Spectral data for the small molecules are reported elsewhere.
  • IR spectra were obtained on a Shimadzu IR Prestige attenuated total reflectance Fourier-transform infrared spectrometer (ATR-IR). Spectra were analyzed using IRsolution software package (Shimadzu). X-ray photoelectron spectroscopy (XPS) measurements were taken with a Kratos Axis Ultra Imaging X-ray photoelectron spectrometer, using Mono A1 anode, 12 kV voltage and 10 mA current.
  • XPS X-ray photoelectron spectroscopy
  • DSC Differential scanning calorimetric
  • Atomic force microscopy was performed under ambient conditions in air.
  • the AFM instrumentation consisted of a MFP-3D-BIO AFM (Asylum Research; Santa Barbara, Calif.) and standard silicon tips (type, OTESPA-70; L, 160 ⁇ m; normal spring constant, 50 N/m; resonance frequency, 246-282 kHz).
  • Force spectroscopy mapping was performed via AFM measurements using a Bruker Multimode 8 system in PeakForceTM tapping mode. This imaging method also provides direct surface maps of modulus, dispersion, deformation and adhesion.
  • the PeakForceTM QNMTM imaging mode uses a modified Hertzian model, the DMT model, to directly extract a reduced Young's modulus (E r ).
  • E r Young's modulus
  • the PeakForceTM QNMTM imaging mode that uses a modified Hertzian model, the DMT 2 model (equation 1), to directly extract a reduced Young's modulus (E r ).
  • the DMT model takes into account surface-tip interactions neglected in the Hertz model.
  • Equation 1 for the DMT reduced Young's Modulus F t is the force on the probe tip, F a is the adhesive force between the probe tip and the sample, R is the working tip radius, and d is the depth of surface deformation below the zero-force contact point.
  • the reduced Young's modulus is related to the sample modulus by equation 2 and reduces to equation 3 where the modulus of the probe tip is much greater than the sample being measured.
  • ⁇ is the sample Poisson's ratio
  • ⁇ t is the probe tip Poisson's ratio
  • E t is the probe tip modulus
  • E is the sample modulus.
  • Force curve fitting after tip contact provides a reduced modulus value.
  • the difference in force curve minima during approach and retraction provides adhesion force.
  • the absolute minimum in tip Z position after contact dictates deformation.
  • the hysteresis in the approach and retraction force curves provides dispersion values.
  • a Mettler Toledo TT-DMA system was used for all dynamic mechanical and dynamic thermal mechanical analysis (DMA/DTMA) studies.
  • Submersion studies were performed in Hyclone (Thermo) calcium/magnesium free phosphate buffered saline solution ( 1 X, PBS) for simulation of an in-vivo environment.
  • Submersion studies were performed in synthetic sea water (Ricca Chemicals, cat. no. 8363-5, ASTM D 1141-substitute ocean water) for simulation of a marine environment. All measurements were taken in compression with a dynamic force of 0.1 N.
  • Bovine serum albumin conjugated to AlexaFluor-680 was dissolved in phosphate buffered saline (PBS) solution (pH 7.1) to a concentration of 0.1 mg/mL and stored in the dark.
  • PBS phosphate buffered saline
  • Sylgard 184 was used as a standard to test against the terpolymer film. The surface of the terpolymer network and Sylgard 184 were incubated in fresh PBS buffer for 10 min and dried via filtered nitrogen gas. The surfaces were then exposed to Alexa-Fluor-680 conjugate in PBS at 0.1 mg mL ⁇ 1 for 45 min in a dark chamber. After exposure, the surfaces were washed with 5 mL of PBS buffer and dried via filtered nitrogen gas for 1 h.
  • Z-stacked confocal fluorescence images were taken of the BSA exposed surfaces and were discussed in terms of resultant intensity histograms.
  • the imaging platform was a full spectral Olympus FV-1000 laser scanning confocal microscope operating with a 635 nm diode laser and fluorescence collection selected by a wide band monochrometer from 650 to 750 nm.
  • HBFP Hyperbranched Fluoropolymer
  • the synthesis scheme is provided in FIG. 1 , and further described below.
  • HBFP-PEG-PDMS networks were prepared with a constant wt % of HBFP (3b) and at varying wt % PEG (0-75 wt %, calculated with respect to the weight of HBFP) and PDMS (25-75 wt %, calculated with respect to the weight of HBFP) to investigate how the relative stoichiometry of the crosslinkers affected surface topography and hydrophilicity.
  • the solution was drop cast (0.5 mL per slide) onto pre-cleaned, pre-cut 1 cm 2 glass microscope slides. A period of ca. 30 min allowed for the solvent to evaporate, which afforded a thick pre-gel that was cured at 110° C. for 45 min under N 2 atmosphere to afford the dry coatings.
  • the crosslinked networks were then submerged in nanopure water bath overnight prior to characterization.
  • HBFP-PDMS binary networks and nine HBFP-PEG-PDMS terpolymer networks was synthesized with varying stoichiometries of the HBFP, PEG (0, 25, 50 and 75 wt %, relative to HBFP) and PDMS (25, 50 and 75 wt %, relative to HBFP) components, to probe the compositional effects on the physical, mechanical and biological properties of the crosslinked materials.
  • the process began through the generation of HBFP by synthesizing the precursor compound 1, having the chemical structure shown below,
  • Deformation mapping at constant force provides an inverse relationship to that observed from modulus mapping, with the stiff island regions deforming 2 nm, the raised portions connecting the island regions deforming 4 nm and the soft, lowered interstitial regions deforming 10 nm at a constant tapping force.
  • Adhesion force mapping provides similar phase information as what might be assumed from topography, while also suggesting that the height of the features may be directly related to the surface energy where the raised regions are lower energy and the lower regions are rich in higher surface energy material.
  • Dissipation mapping provides information about the energy loss to non-restorative forces after deformation, and correlates with deformation. From what is known about fluoropolymer, PDMS and PEG surfaces in general, the following assignments are made:
  • ATR-IR attenuated total reflectance infrared spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • TP was investigated by thermogravimetric analysis to determine how crosslinking influences the thermal stability of the network ( FIG. 8 ). From ambient temperature to 250° C., 5% mass loss is seen in the network, consistent with a partial degradation of PDMS. There are then two degradation events that can be seen in the network, the first occurring from 250° C. to ca. 350° C. corresponding to a continued degradation of PDMS, and then from 350° C. to 500° C. resulting in an 80% mass loss of the sample in total, corresponding to the decomposition of HBFP and PEG. It can be seen through this study that the crosslinks in the system do not infer any additional thermal benefit to the network, but overall, this finding should not detract from the intended uses for this material.
  • FIGS. 9A and 9B Differential scanning calorimetry was used to probe the phase transitions present in the terpolymer network ( FIGS. 9A and 9B ).
  • a melting transition can first be seen at 33° C. which can be attributed to the PEG in the network followed by a T g at 63° C. which can be attributed to HBFP.
  • a third phase transition, a T g is then seen at 113° C. which is also attributed to HBFP.
  • HBFP has two unique glass transition temperatures arising from the two units that comprise the framework of the polymer.
  • the T g at 63° C. is most likely from the branching in the polymer framework in HBFP, with the second T g arising from linear pentafluorostyrene units.
  • TP The mechanical properties of TP were investigated with a combination of dynamic mechanical analysis (DMA), dynamic thermal mechanical analysis (DTMA) and static stress-strain analysis.
  • DMA dynamic mechanical analysis
  • DTMA dynamic thermal mechanical analysis
  • static stress-strain analysis The mechanical properties of TP were investigated with a combination of dynamic mechanical analysis (DMA), dynamic thermal mechanical analysis (DTMA) and static stress-strain analysis.
  • Initial investigation of TP by DTMA at 1 Hz ( FIG. 10 ) showed two phase transitions via tan ⁇ peaks at 89 (A1) and 129° C. (A2), which were assigned to a glass transition of the PEGylated fluorostyrene branching subunits and of the pentafluorosytrene subunits of the HBFP respectively.
  • Room temperature (A0) storage modulus (E′) was found to be 7.1 MPa with a loss modulus (E′′) of 1.1 MPa.
  • a quasi-steady state character was reached near 150° C.
  • This system also has potential application as a coating on biomedical devices where a decreased likelihood of vector transferal or human cell adhesion is sought. Therefore assessment of the mechanical response of the TP was performed at conditions that simulate an in-body environment. DMA was performed in a submersion of PBS at 37° C. (B0) and monitored to observe solvent uptake (B1 & B2), swelling (B3) and the steady state (B4) response of the film after reaching solvent equilibrium ( FIG. 12 ). Two (relatively) fast phases of initial solvent uptake are observed with transition lifetimes of 0.03 and 0.12 h, and are assigned to rapid association of PEG domains and amphiphilic HBFP domains respectively. These processes resulted in a total loss of ca. 65% of film stiffness.
  • the synthesized terpolymer system expands on the current generation of coatings and displays distinctive topographical, compositional and morphological features, as seen specifically through the analysis of the surfaces by surface force and ATR-IR spectroscopies.
  • the systems presented here provide enhanced surface complexity with no significant increase in the synthetic or cure conditions.
  • This system also provides an entirely new mode of dynamic surface reorganization as shown by preferential emergence of PDMS character on the surface after water immersion and differing from the heavy fluoropolymer expression observed in previous HBFP-PEG formulations.
  • compositional ratios of the three constituents By varying the compositional ratios of the three constituents, a wide range of topographical, hydroscopic and swell-reorganization variations were displayed. Microscopic characterization revealed a highly disordered heterogeneous surface that varied both topographically and chemically at the micro- and nano-scale. Investigation of non-specific protein binding resistance of the terpolymer network is encouraging; with significantly better resistance to protein adsorption than a commercially available anti-biofouling PDMS standard.
  • Anti-biofouling surfaces were produced by synthesis of terpolymer coatings composed of hyperbranched fluoropolymers crosslinked with bisamino-propyl poly(ethylene glycol) and bisamino-propyl polydimethylsiloxane (PDMS).
  • This HBFP was chosen, due to its amphiphilic character, which enhances anti-biofouling performance while retaining the desired nanoscale surface heterogeneities.
  • Crosslinking in this system occurred via a substitution reaction of the bromoacetyl and bromobenzyl groups of HBFP with the amine termini of both the linear PEG and PDMS crosslinkers.
  • Nanoscale imaging and surface spectroscopy confirmed that this system possessed complex surface topographies and chemical compositions.
  • HBFP-PEG-PDMS An array of HBFP-PEG-PDMS were produced to investigate the anti-biofouling performance of the coatings.
  • the amounts of the crosslinkers were varied with respect to HBFP to create a 3 ⁇ 3 array of coatings with varying weight percentages of PEG and PDMS (25 wt %, 50 wt % and 75 wt %) to determine which composition and properties afford the most promising characteristics for future anti-biofouling coatings.
  • a range of test coatings were prepared for evaluation. Coatings were mounted on an epoxy barrier coat (Interseal 670HS). Generally, the two component system of Interseal 670HS was mixed per the manufacturer's instructions (5.70 mL:1 mL of Part A:Part B) and was then diluted with 3 mL of THF. The system was applied to a glass microscope slides via an airbrush applicator (Central Pneumatic) using an application pressure of 50 psi. The system allowed to cure at ambient temperature for 18 hours.
  • an airbrush applicator Central Pneumatic
  • HBFP 370 mg, 0.032 mmol
  • 1500 Da bis(3-aminopropyl)-terminated PEG 92.5 mg, 0.062 mmol, 25 wt %)
  • 1500 Da bis(3-aminopropyl)-terminated PDMS 92.5 mg, 0.037 mmol, 25 wt %)
  • THF 20 mL
  • DIPEA N,N-diisopropylethylamine
  • the film was then cured in an oven at 110° C. for 45 min under N2 atmosphere to afford the dry coatings.
  • Slides coated with only the barrier coat (under-coat) were supplied as a control to check that it was not affecting the attachment of the diatoms. Water contact angles for the coatings were evaluated to estimate hydrophobicity.
  • N incerta cells were cultured in F/2 medium contained in 250 ml conical flasks. After 3 days the cells were in log phase growth. Cells were washed 3 times in fresh medium before harvesting and diluted to give a suspension with a chlorophyll a content of approximately 0.25 ⁇ g ml ⁇ 1. Cells were settled in individual dishes containing 10 ml of suspension at room temperature on the laboratory bench. After 2 hours the slides were exposed to a submerged wash in seawater to remove cells which had not attached (the immersion process avoided passing the samples through the air-water interface). Samples were fixed in 2.5% glutaraldehyde, air dried and the density of cells attached to the surface was counted on each slide using a fluorescence microscope. Strong autofluorescence from the samples meant that counting could not be automated and counts were made by eye. Counts were made for 10 fields of view (each 0.15 mm2) on each slide. Results are shown in FIG. 14 .
  • Zoospores were obtained from mature plants of U. linza by the standard method. A suspension of zoospores (10 ml; 1 ⁇ 106 spores ml ⁇ 1) was added to individual compartments of quadriperm dishes containing the samples. After 45 minutes in darkness at room temperature, the slides were washed by passing 10 times through a beaker of seawater to remove unsettled (i.e. swimming) spores. Slides were fixed using 2.5% glutaraldehyde in seawater. The density of zoospores attached to the surface was counted on each of 3 replicate slides using an image analysis system attached to a fluorescence microscope. Spores were visualised by autofluorescence of chlorophyll. Counts were made for 30 fields of view (each 0.15 mm 2 ) on each slide. Results are shown in FIG. 17 .
  • Spores were allowed to settle on the coatings for 45 minutes and then washed as described above.
  • the spores were cultured using supplemented seawater medium for 7 days to produce sporelings (young plants) on 6 replicate slides of each treatment. Sporeling growth medium was refreshed every 48 hours.
  • Sporeling biomass was determined in situ by measuring the fluorescence of the chlorophyll contained within the sporelings in a Tecan fluorescence plate reader. Using this method the biomass was quantified in terms of relative fluorescence units (RFU).
  • RFU relative fluorescence units
  • the RFU value for each slide is the mean of 70 point fluorescence readings taken from the central portion.
  • the sporeling growth data are expressed at FIG. 18 as the mean RFU of 6 replicate slides; bars show SEM (standard error of the mean).
  • the process of washing removes unattached and weakly attached cells and thus differences in initial attachment density reflect differences in the ability of cells to attach firmly to the surfaces and resist the hydrodynamic forces of washing.
  • the initial attachment densities of diatoms were broadly similar on all the terpolymer test coatings ( FIG. 14 ). Attachment densities were higher on the glass standard and on the Interseal undercoat.
  • Diatom removal due to a shear stress of 20 Pa was higher from the three coatings containing PEG at 75 wgt % than from the other coatings ( FIG. 15 ). Removal was exceptionally low from the coatings containing PEG at 25 and 50 wgt % in conjunction with PDMS at 50 wgt %.
  • the density of diatoms remaining on the terpolymer coatings was lowest on the coatings containing PEG at 75 wgt % in conjunction with PDMS at 50 and 75 wgt % ( FIG. 16 ).
  • FIGS. 20A and 20B Biomass generation on all coatings broadly reflected the spore settlement densities described above ( FIG. 18 ). Sporeling growth appeared normal on all coatings with no signs of toxicity ( FIGS. 20A and 20B ) (from left, the coatings illustrated in FIGS. 20A and 20B are: Control; PEG 25+PD 25, 50, 75; PEG 50+PD 25, 50, 75; PEG 75+PD 25, 50, 75).
  • the percent removal of sporelings is shown in FIG. 19 . None of the coatings had a fouling-release performance that was as good as the PDMSe standard. Adhesion strength on the PEG 25 coatings was similar at all PDMS loadings. On the PEG 50 coatings adhesion strength decreased with PDMS content i.e. % removal increased as PDMS content increased. On the PEG 75 coatings adhesion strength was slightly higher (i.e. less removal) on the PDMS 50% loading than on the 25 and 75% loadings.

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